Z-otloro-j-iminobutyronitrile



Patented Jan. 13, 1948 2-CHLORO-3-IMINOBUTYRONITRILE AND PROCESS Jerome L. Mostek, Chicago. Ill., assignor to Sinclair Refining Company, New York, N. Y., a

corporation of Maine No Drawing. Application October 10, 1945, Serial No. 621,607

3 Claims. (Cl. 260-464) This invention relates to 2-chloro-3-iminobutyronitrile, and to readily prepared products of hydrolysis thereof, namely, 2-chloro-3-ketobutyronitrile and 2-chloro-3-ketobutyramlde.

The invention includes a new process of preparing these compounds. which consists in the treatment of 2,2,3-trichlorobutyronltrile with liquid ammonia. The new process is applicable to the production of other 2-chloro-3-imlnonitriles having in excess of four carbon atoms.

The 2-chloro-3-iminobutyronitrile is a crystalline product, melting at 116-117 0.; useful, among other purposes. for preparing the corre-- sponding ketonitrile, ketoamlde, and the 2-chloroketo esters. The 2-chlormS-ketobutyronitrile is a liquid. boiling at 185-187 C. (103 C./50 mm.). The 2-chloro-3-ketobutyramide is a white crystalline product melting at 76-77" C.

The invention will be illustrated by the following example, but it is not limited thereto.

Example-To liquid ammonia in a bomb reactor is gradually added 2,2.3-trichlorobutyronitrile, the molar ratio of ammonia to nitrile being about 15 to 1. The mixture is permitted to stand at room temperature. about 25 C., for 17 hours. Excess ammonia is then removed by reducing the pressure, and the residue remaining in the bomb extracted with absolute ethyl alcohol. Ammonium chloride remains as a residue. The filtrate is concentrated under vacuum. On the addition of water, crystals form and precipitate from the solution. 2-ch1oro-3-lminobutyronltrile is obtained in good yield. On recrystallization from water, a product with a. melting point of 116-l17 C. is obtained.

The crude reaction product is treated with a concentrated hydrochloric acid at 5 C. The solid product which first forms gradually becomes a heavy liquid, and the reaction mixture forms two layers. fractionatlng. 2-chloro-3-ketobutyronitrile is obtaine in good yield.

Careful hydrolysis of the 2-chloro-3-lminobutyronitrile with equimolar proportions of concentrated sulfuric acid and water gives 2-chloro- 3-ketobutyramide, M. P. 76-'l7 0., in good yield.

Refluxing of the 2-chloro-3-ketobutyronltrile 2 of the invention with concentrated sulfuric acid and an excess of absolute ethyl alcohol for a substantial period, for example, 11 hours, followed by removal of the alcohol by distillation, the addition of water, extraction with ether. drying and fractionating gives 2-ch1oroacetoacetic ethyl ester, a valuable intermediate, boiling point 193-197 C., in good yield.

By the treatment of other 2.2.3-trlchloronitriles with liquid ammonia, such as 2.2,3-trichlorovaleronitrile and 2.2.3-trlchlorocapronltrlle, the

corresponding higher imino nltriles are obtained.

I laim:

1. 2.-chloro-3-lminobutyronitrlle.

2. In a process for preparing 2-chloro-3-imlnobutyronitrile the step which comprises reacting 2,2,B-trichIorobutyronitrile with liquid anhydrous ammonia.

3. In a process for producing 2-chloro-3-iminonitriles having at least four carbon atoms. the

On extraction with ether, drying and step which comprises reacting a compound of the formula REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,992,615 Hoffman et al Feb. 26. 1935 2,109,929 Rigby Mar. 1, 1938 2,163,594 Engels et a1 June 27, 1939 OTHER REFERENCES Keil, Chemical Abstracts, vol. 22. p. 385 (1928).

Quillco' et al., Chemical Abstracts. vol. 32, col. 7455 1938).

Hilton et al., Jour. Chem. Soc., vol. 1937, pp. 922-929. 

